The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Local and Parallel Finite Element Algorithms for Eigenvalue Problems

Abstract Some new local and parallel finite element algorithms are proposed and analyzed in this paper foreigenvalue problems.With these algorithms, the solution of an eigenvalue problem on a fine grid is reduced tothe solution of an eigenvalue problem on a relatively coarse grid together with solutions of some linear algebraicsystems on fine grid by using some local and parallel procedure.A theoretical tool for analyzing these algorithmsis some local error estimate that is also obtained in this paper for finite element approximations of eigenvectorson general shape-regular grids.     

Affine-scaling for linear programs with free variables

The affine-scaling modification of Karmarkar's algorithm is extended to solve problems with free variables. This extended primal algorithm is used to prove two important results. First the geometrically elegant feasibility algorithm proposed by Chandru and Kochar is the same algorithm as the one obtained by appending a single column of residuals to the constraint matrix. Second the dual algorithm as first described by Adler et al., is the same as the extended primal algorithm applied to the dual.     

Kalman filtering of a space-time Markov random field

In this paper, finite-dimensional recursive filters for space-time Markov random fields are derived. These filters can be used with the expectation maximization (EM) algorithm to yield maximum likelihood estimates of the parameters of the model.     

Generic entangling through quantum indistinguishability

We present a general scheme for entangling any degree of freedom of two uncorrelated identical particles from independent sources by a combination of two-particle interferometry and which-way detection. We show that this entanglement generation procedure works for completely random initial states of the variable to be entangled. We also demonstrate a curious complementarity exhibited by our scheme and its applications in estimating the generated entanglement as a function of wave packet overlap at the beamsplitter.     

On Quantum Team Games

Recently Liu and Simaan (2004) convex static multi-team classical games have been introduced. Here they are generalized to both nonconvex, dynamic and quantum games. Puu's incomplete information dynamical systems are modified and applied to Cournot team game. The replicator dynamics of the quantum prisoner's dilemma game is also studied.     

Field Theory Methods in Classical Dynamics

A Dirac picture perturbation theory is developed for the time evolution operator in classical dynamics in the spirit of the Schwinger–Feynman–Dyson perturbation expansion and detailed rules are derived for computations. Complexification formalisms are given for the time evolution operator suitable for phase space analyses, and then extended to a two-dimensional setting for a study of the geometrical Berry phase as an example. Finally a direct integration of Hamilton's equations is shown to lead naturally to a path integral expression, as a resolution of the identity, as applied to arbitrary functions of generalized coordinates and momenta.     

Highly accurate calculation of radial spheroidal functions

A new method for calculating the radial spheroidal functions of the first kind is proposed for the arguments that are greater than unity in modulus. A well-known representation of these functions is refined and used for this purpose. The constructs and the software implementation proposed in the paper provide an efficient tool for the calculation of the functions with a desired accuracy in a wide range of parameters.